Fluorine-containing mono- or poly-alkylene glycol and method for producing same

ABSTRACT

The novel fluorine-containing mono- or poly-alkylene glycol of this invention is a mono- or poly-alkylene glycol of the formula (I): ##STR1## wherein R 1 , R 2  and R 3  independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, A represents a hydrogen atom, an unsaturated hydrocarbon group having 1 to 30 carbon atoms, a polar group or a polar group substituted with an unsaturated hydrocarbon group having 1 to 100 carbon atoms, B represents the same as the group selected from the group of A, provided that both A and B are not hydrogen atom, or a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom or fluorine atom, x represents an integer of 0 to 100, and n represents an integer of 1 to 1000, the mono- or poly-oxyalkylene group in the main chain of the mono- or poly-alkylene glycol having at least one fluorine-substituted hydrocarbon group with 2 to 30 carbon atoms having at least 3 fluorine atoms bonded thereto graft-bonded onto the mono- or poly-oxyalkylene group in the main chain of the mono- or poly-alkylene glycol per one molecule of the mono- or poly-alkylene glycol.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel fluorine-containing mono- orpoly-alkylene glycol and a method for producing the same, moreparticularly it relates to a novel fluorine-containing mono- orpoly-alkylene glycol to be used and the starting material in producing apolymer having an excellent oxygene permeability, water swellability andcontamination resistance, and a method for producing the same.

2. Description of the Related Art

A polymer constituting a contact lens must have oxygen permeability, andas the material for such a lens, a polymer obtained by polymerization ofa monomer such as methyl methacrylate or a methacrylic acid ester typecompound has been used in the prior art. Nevertheless, most of thesepolymers have an inferior oxygen permeability and a lens made of such apolymer can not be worn for a long time.

To improve the oxygen permeability of a methacrylic acid ester polymer,it has been proposed to make contact lenses of a silicone methacrylatetype polymer having siloxane bonds introduced into methacrylic acidester molecules (see, for example, Japanese Patent Publication (Kokoku)No. 52-33502), of an oxygen permeable polymer composed mainly ofcellulose acetate butyrate, and of a fluorine-containing methacrylatetype polymer (see, for example, Japanese Unexamined Patent Publications(Kokai) Nos. 57-51705 and 61-111308). Although these polymers have animproved oxygen permeability, compared with the methacrylic acid estertype polymers such as polymethyl methacrylate of the prior art, they arestill not satisfactory, and polymers having a further improved oxygenpermeability are required. Also, these polymers do not have asatisfactory contamination resistance, hydrophilic property, and waterswellability.

SUMMARY OF THE INVENTION

Accordingly, the objects of the present invention are to eliminate theabove-mentioned problems of the prior art and to provide a novelfluorine-containing mono- or poly-alkylene glycol which can be used forpreparing a polymer having an excellent oxygen permeability and anexcellent hydrophilic property, water swellability, and contaminationresistance, and to provide a method for producing the same.

Other objects and advantages of the present invention will be apparentfrom the following description.

In accordance with the present invention, there is provided afluorine-containing mono- or poly-alkylene glycol derivative of theformula (I): ##STR2## wherein R¹, R² and R³ independently represent ahydrogen atom, or an alkyl group having 1 to 30 carbon atoms, Arepresents a hydrogen atom, an unsaturated hydrocarbon group having 1 to30 carbon atoms, a polar group or a polar group substituted with anunsaturated hydrocarbon group having 1 to 100 carbon atoms, B representsthe same as the group selected from the group of A, provided that both Aand B are not hydrogen atom, or a hydrocarbon group having 1 to 30carbon atoms which may contain oxygen atom or fluorine atom, xrepresents an integer of 0 to 100, and n represents an integer of 1 to1000, the mono- or poly-oxyalkylene group in the main chain of the mono-or poly-alkylene glycol having at least one fluorine-substitutedhydrocarbon group with 2 to 30 carbon atoms having at least 3 fluorineatoms bonded thereto graft-bonded onto the mono- or poly-oxyalkylenegroup in the main chain of the mono- or poly-alkylene glycol per onemolecule of the mono- or poly-alkylene glycol.

In accordance with the present invention, there is also provided anmethod for producing a novel fluorine-containing mono- or poly-alkyleneglycol comprising, obtaining a fluorine-containing mono- orpoly-alkylene glycol of the formula (II) or (III): ##STR3## wherein eachof R¹, R² and R³ represents a hydrogen atom, an alkyl group having 1 to30 carbon atoms, R⁴ represents a hydrocarbon group having 1 to 30 carbonatoms which may also contain an oxygen atom or fluorine atom, xrepresents an integer of 0 to 100, x' represents an integer of 1 to 100,and m and p each represent an integer of 1 to 1000, the mono- orpoly-oxyalkylene group in the main chain of the mono- or poly-alkyleneglycol having at least one fluorine-substituted hydrocarbon group with 2to 30 carbon atoms having at least 3 fluorine atoms bonded theretograft-bonded onto the mono- or poly-oxyalkylene group in the main chainof the mono- or poly-alkylene glycol per one molecule of the mono- orpoly-alkylene glycol, by allowing a mono- or poly-alkylene glycolrepresented by the above formula to react with a fluorine-substitutedunsaturated hydrocarbon having 2 to 30 carbon atoms with at least 3fluorine atoms bonded thereto.

In accordance with the present invention, there is further provided amethod for producing the novel fluorine-containing mono- orpoly-alkylene glycol derivative of the formula (IV): ##STR4## whereinR¹, R² and R³ independently represent a hydrogen atom, an alkyl grouphaving 1 to 30 carbon atoms, A' represents an unsaturated hydrocarbongroup having 1 to 30 carbon atoms, a polar group or a polar groupsubstituted with an unsaturated hydrocarbon group having 1 to 100 carbonatoms, B' represents the same as the group selected from the group of A'or a hydrocarbon group having 1 to 30 carbon atoms, x represents aninteger of 0 to 100, and n represents an integer of 1 to 1000, the mono-or poly-oxyalkylene group in the main chain of the mono- orpoly-alkylene glycol having at least one fluorine-substitutedhydrocarbon group with 2 to 30 carbon atoms having at least 3 fluorineatoms bonded thereto, graft-bonded onto the mono- or poly-oxyalkylenegroup in the main chain of the mono- or poly-alkylene glycol per onemolecule of the mono- or poly-alkylene glycol, which comprises allowinga mono- or poly-alkylene glycol represented by the formula (III):##STR5## wherein R₁, R₂ and R₃ independently represent a hydrogen atomor an alkyl group having 1 to 30 carbon atoms, X represents an integerof 0 to 100 and n an integer of 1 to 1000 to react with afluorine-substituted unsaturated hydrocarbon having 2 to 30 carbon atomswith at least 3 fluorine atoms bonded thereto to obtain afluorine-containing mono- or poly-alkylene glycol having thefluorine-substituted hydrocarbon group derived from at least onefluorine-substituted unsaturated hydrocarbon graft-bonded onto the mono-or poly-oxyalkylene group in the main chain of the mono- orpoly-alkylene glycol per one molecule of the mono- or poly-alkyleneglycol, and subsequently allowing the fluorine-containing mono- orpoly-alkylene glycol to react with one or two or more kinds of a polargroup containing organic compounds.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be better understood from the description setforth below with reference to the accompanying drawing of FIG. 1, whichshows an IR absorption chart of one example of the novelfluorine-containing polyalkylene glycol derivative according to thepresent invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The novel fluorine-containing mono- or poly-alkylene glycol and themethod for producing the same according to the present invention are nowdescribed in detail.

The novel fluorine-containing mono- or poly-alkylene glycol according tothe present invention has at least one fluorine-substituted hydrocarbongroup with 2 to 30 carbon atoms having at least 3 fluorine atoms bondedthereto grafted onto the mono- or poly-oxyalkylene group in the mainchain of the mono- or poly-alkylene glycol represented by theabove-mentioned formula (I) or the above-mentioned formulae (II), (III),and (IV).

In the above-mentioned general formulae, R¹, R² and R³ each represent ahydrogen atom or an alkyl group having 1 to 30 carbon atoms, andspecific examples of the alkyl group may include methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl groups.

A represents a hydrogen atom, an unsaturated hydrocarbon group, a polargroup or a polar group substituted with an unsaturated hydrocarbon grouphaving 1 to 100 carbon atoms.

Specific examples of such an unsaturated hydrocarbon group may include avinyl group, allyl group, isopropenyl group, etc.

Specific examples of the polar group may include an aminocarbonyl group;H₂ N--CO--, etc.

Further, the polar group substituted with an unsaturated hydrocarbongroup may be exemplified by an acryloyl group (CH₂ ═CHCO--),methacrylolyl group (CH₂ ═C(CH₃)CO--), etc., preferably an acryloylgroup or methacryloyl group.

B represents the same group as that selected from the group of A asdescribed above or a hydrocarbon group having 1 to 30 carbon atoms whichmay contain an oxygen atom or fluorine atom. Specific examples of thehydrocarbon group may include alkyl groups such as methyl, ethyl,propyl, isopropyl butyl, isobutyl, sec-butyl, tert-butyl, and pentylgroups.

R⁴ in the above formula (II) represents a hydrocarbon group having 1 to30 carbon atoms, which preferably may also contain 0 to 61 oxygen atomsor fluorine atoms. More specifically, there may be included, --CH₃, --C₂H₅, --C₄ H₉, --C₆ H₁₂, --C₁₀ H₂₁, --C₁₂ H₂₅, --C₁₇ H₃₅, --C₂₀ H₄₁,--CH(CH₃)₂, --C₆ H₄ C₉ H₁₉, --COC₁₇ H₃₅, CF₂ CFH(CF₂)₆ H, --COCF₃,--COC₂ F₅, --COCH(CF₃)₂, --COC₇ F₁₅, --COC₁₀ F₂₁, --COCH₂ CH₂ C₇ F₁₅,--COCH₂ CF₃

In the above-mentioned formulae, x is in the range of 0 to 100,preferably 0 to 30, and m, n and p are each in the range of 1 to 1000,preferably 1 to 500.

Specific examples of the mono- or poly-alkylene glycol represented bythe above formula (I) according to the present invention may include thefollowing compounds: ##STR6## and mixtures thereof.

Other specific examples of the mono- and poly-alkylene glycolrepresented by the above formula (I) may include the followingcompounds: ##STR7## and mixtures thereof.

Further specific examples of the mono- or poly-alkylene glycolderivative represented by the above formula (I) according to the presentinvention may include mono- or poly-alkylene glycol derivativessubstituted at the terminal ends with unsaturated hydrocarbon groups,such as: ##STR8## mono- or poly-alkylene glycol derivatives substitutedat the terminal ends with polar groups, such as: ##STR9## (meth)acrylicacid ester type mono- or poly-alkylene glycol derivatives, such as:##STR10##

Specific examples of the fluorine-substituted hydrocarbon group having 2to 30 carbon atoms with at least 3 fluorine atoms bonded thereto to begraft bonded onto such a mon- or poly-alkylene glycol of the formula (I)as described above may include the compounds shown below: ##STR11##

Preferably, the fluorine-substituted alkyl group has 2 to 20 carbonatoms with at least 3 fluorine atoms bonded thereto.

The fluorine-substituted hydrocarbon group is graft bonded to thealkylene group of the oxyalkylene group in the main chain of the mono-or poly-alkylene glycol represented by the above formula (I), and thegrafting ratio of the fluorine-substituted hydrocarbon group is at leastone, preferably 1 to 20 per one molecule of the mono- or poly-alkyleneglycol, with the result that the fluorine-containing mono- orpoly-alkylene glycol obtained has 3 to 400, preferably 3 to 200 fluorineatoms, per one molecules.

The fluorine-substituted hydrocarbon group having 2 to 30 carbon atomswith at least 3 fluorine atoms bonded thereto can be introduced into thecompound represented by the formula (I) by allowing afluorine-substituted unsaturated hydrocarbon having 2 to 30 carbon atomswith at least 3 fluorine atoms bonded thereto to react with a mono- orpoly-alkylene glycol.

Examples of the fluorine-substituted unsaturated hydrocarbon asdescribed above include the following compounds: ##STR12##

The novel fluorine-containing mono- or poly-alkylene glycol according tothe present invention is a compound having at least onefluorine-substituted hydrocarbon group having 2 to 30 carbon atoms withat least 3 fluorine atoms bonded thereto as described above graft-bondedonto the mono- or poly-oxyalkylene group in the main chain of the mono-or poly-alkylene glycol per one molecule of the mono- or poly-alkyleneglycol derivative, and specific examples thereof include the following(meth)acrylic acid ester type fluorine-containing mono- or poly-alkyleneglycol derivatives: ##STR13## Here, p and q are integers and p+q is 1 to1000. ##STR14## show random sequences, hereinafter the same. ##STR15##Further examples are as follows: ##STR16##

In the present invention, the fluorine-containing mono- or poly-alkyleneglycol as described above can be produced according to the method asdescribed below.

By allowing the mono- or poly-alkylene glycol as described aboverepresented by the formulae (II) and (III): ##STR17## wherein R¹, R² andR³ independently represent a hydrogen atom or an alkyl group having 1 to³⁰ carbon atoms, R⁴ represents a hydrocarbon group having 1 to 30 carbonatoms which may also contain an oxygen atom or fluorine atom, xrepresents an integer of 0 to 100, and m and p each represent an integerof 1 to 1000, to react with the fluorine-substituted unsaturatedhydrocarbon having 2 to 30 carbon atoms with at least 3 fluorine atomsbonded thereto as described above, a mono- or polyalkylene glycol havingat least one fluorine-substituted hydrocarbon group with 2 to 30 carbonatoms having at least one fluorine-substituted hydrocarbon group derivedfrom the fluorine-substituted unsaturated hydrocarbon graft-bonded ontothe mono- or poly-oxyalkylene group in the main chain of the mono- orpoly-alkylene glycol per one molecule of the mono- or poly-alkyleneglycol is obtained.

Furthermore, in the present invention, the fluorine-containing mono- orpoly-alkylene glycol as described above can be produced according to themethod as described below.

First, by allowing the mono- or poly-alkylene glycol as described aboverepresented by the formulae (II): ##STR18## wherein R¹, R² and R³independently represent a hydrogen atom or an alkyl group having 1 to 30carbon atoms, R⁴ represents a hydrocarbon group having 1 to 30 carbonatoms which may also contain oxygen atom or fluorine atom, x representsan integer of 0 to 100, and p represents an integer of 1 to 1000, toreact with the fluorine-substituted unsaturated hydrocarbon having 2 to30 carbon atoms with at least 3 fluorine atoms bonded thereto asdescribed above, a mono- or poly-alkylene glycol having at least onefluorine-substituted hydrocarbon group with 2 to 30 carbon atoms havingat least one fluorine-substituted hydrocarbon group derived from thefluorine-substituted unsaturated hydrocarbon graft bonded onto the mono-or poly-oxyalkylene group in the main chain of the mono- orpoly-alkylene glycol per one molecule of the mono- or poly-alkyleneglycol is prepared.

The reactions of the above mono- or poly-alkylene glycol with the abovefluorine-substituted unsaturated hydrocarbon are carried out generallyin the presence of a reaction initiator and a solvent. The reactioninitiator to be used in carrying out the reaction specifically includesisobutyryl peroxide, 1-hexyl-peroxyneohexanoate,2,4-dichlorobenzoylperoxide, octanoylperoxide, cumylperoxyoctoate,m-toluoylperoxide, benzoylperoxide, t-butylperoxyacetate,t-butylperoxybenzoate, t-butylcumylperoxide, di-tertiary-butylperoxide,t-butyl hydroperoxide, etc., and may be used in an amount of 0.1mmol/liter to 10 mol/liter, preferably 10 mmol/liter, to 1 mol/liter.

Specific examples of the solvent to be used in the reaction includebenzene, toluene, xylene, chlorobenzene, dichlorobenzene,benzotrifluoride, chlorobenzotrifluoride, xylene hexafluoride, etc.

The reaction may be carried out at 20° to 300° C., preferably 50° to200° C., for 2 to 50 hours.

After completion of the reaction, the fluorine-containing mono- orpoly-alkylene glycol is separated according to the following treatment.Namely, if the product is a liquid fluorine-containing mono- orpolyalkylene glycol having a low molecular weight, the product can bedistilled, or extracted by a solvent mixture of water and diethyl etherinto diethyl ether, followed by concentration and distillation, toseparate the fluorine-containing mono- or poly-alkylene glycol formed.If the product is a solid having a high molecular weight, separation canbe effected only by concentrating the reaction product to evaporate thesolvent and unreacted fluoroolefin.

Consequently, in the present invention, the fluorine-containing mono- orpoly-alkylene glycol is allowed to react with one or two or more kindsof polar group containing organic compounds to obtain afluorine-containing mono- or polyalkylene glycol derivative as describedabove having terminal hydroxyl groups of the fluorine-containing mono-or poly-alkylene glycol substituted with other groups as describedabove. Specific examples of the polar group containing organic compoundsto be used during this reaction include: ##STR19##

EXAMPLES

The present invention will now be further illustrated by, but is by nomeans limited to, the following Examples.

Example 1-1

A 100 ml stainless steel autoclave was charged with 20 g of ethyleneglycol, 0.5 g of di-tert-butyl peroxide and 10 ml of benzotrifluoride asa solvent, tightly sealed, and then 10 g of hexafluoropropylene wascharged into the reactor under pressure and the reaction was carried outunder a pressure of 50 kg/cm² of nitrogen, while stirring at 140° C. for5 hours.

After completion of the reaction, the mixture was cooled and gas purgedtherefrom, and the reaction mixture then withdrawn from the reactor. Thereaction mixture was concentrated under a reduced pressure and thesolvent evaporated. Extraction with diethyl ether and water washing wasrepeatedly conducted, and the ether layer was separated, followed byconcentration, to isolate a crude product with a purity of 94%(according to gas chromatography). The product obtained was thendistilled under a reduced pressure to obtain 8.5 g of1,2-dihydroxy-3,3,4,5,5,5-hexafluoropentane with a purity of 98%(according to gas chromatography) (yield based on hexafluoropropylene:60.1 mol %).

The compound obtained had the following physical properties andanalytical results.

Boiling point: 58°-60° C./3-4 mmHg

    ______________________________________                                        Elemental analytical values:                                                           C (%)      H (%)   F (%)                                             ______________________________________                                        Calculated 28.30        2.83    53.77                                         Found      27.8         2.5     52.9                                          ______________________________________                                    

Gas chromatographic mass analysis:

According to the FI method the molecular ion peak mass was 213.

IR Absorptions observed at νOH 3350 cm⁻¹, νCF 1200 cm⁻¹.

¹ H-NMR: (solvent for measurement: CD₃ OD)

δ+3.80 (ethylene glycol portion --CH₂ --)

δ=4.80 (ethylene glycol portion --CH--)

δ=5.24 Doublet-multiplet (--CFH--² J_(HF) =42 Hz, ³ J_(HF) =7 Hz)

From the analytical results shown above, the product was confirmed tohave the structure ##STR20##

Examples 1-2 to 1-4

The same procedures as in Example 1-1 were conducted, except that thekind of alkylene glycol used in Example 1-1 was changed. The results areshown in Table 1-1.

Example 1-5

The reaction was conducted as in Example 1-1, except the kind ofalkylene glycol, the kind of fluoroolefin, and the initiator in Example1-1 were changed. The reaction product was concentrated under a reducedpressure and the reaction starting material was evaporated to isolate areaction product. The results are shown in Table 1-1.

                                      TABLE 1-1                                   __________________________________________________________________________                                        Reaction                                                                      conditions                                Ex-                                                                              Reaction material             Sol-                                                                             Temper-                                   am-            Fluorine compound                                                                        Initiator                                                                            vent                                                                             ature                                                                              Time                                 ple                                                                              Alkyleneglycol (g)                                                                        (g)        g      ml (°C.)                                                                       h  Product                           __________________________________________________________________________    1-2                                                                              Triethyleneglycol                                                                      25.0                                                                             CF.sub.2 ═CF.CF.sub.3 15                                                             di-t-butyl                                                                         0.8                                                                             -- 140  5  HOCH.sub.2 CHOCH.sub.2                                                        CH.sub.2 OCH.sub.2 CH.sub.2                                                   OH                                                          peroxide            CF.sub.2 CHFCF.sub.3                                                        HOCH.sub.2 CH.sub.2 OCHCH.sub.                                                2 OCH.sub.2 CH.sub.2 OH                                                           CF.sub.2 CHFCF.sub.3                                                      HOCHCH.sub.2 OCH.sub.2                                                        CH.sub.2 OCH.sub.2 CH.sub.2                                                   OH                                                                             CF.sub.2 CHFCF.sub.3             1-3                                                                              Methylcellosolve                                                                       13 CF.sub.2 ═CF.CF.sub.3 14                                                             di-t-butyl                                                                         0.8                                                                             -- 140  5  HOCHCH.sub.2 OCH.sub.3,                                                       HOCH.sub.2 CHOCH.sub.3                                      peroxide           CF.sub.2 CHFCF.sub.3                                                         CF.sub.2 CHFCF.sub.3                                                          HOCH.sub.2 CH.sub.2 OCH.sub.2                                                 CF.sub.2 CHFCF.sub.3              1-4                                                                              Triethyleneglycol                                                                      25 CF.sub.2 ═ CF.CF.sub.3 15                                                            di-t-butyl                                                                         0.8                                                                             -- 140  5  HOCH.sub.2 CHOCH.sub.2                                                        CH.sub.2 OCH.sub.2 CH.sub.2                                                   OCH.sub.3                            monomethylether        peroxide            CF.sub.2 CHFCF.sub.3                                                        HOCH.sub.2 CH.sub.2 OCHCH.sub.                                                2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                    CF.sub.2 CHFCF.sub.3                                                      HOCH.sub.2 CH.sub.2 OCH.sub.2                                                 CHOCH.sub.2 CH.sub.2 OCH.sub.3                                                     CF.sub.2 CHFCF.sub.3                                                     HOCH.sub.2 CH.sub.2 OCH.sub.2                                                 CH.sub.2 OCHCH.sub.2 OCH.sub.3                                                      CF.sub.2 CHFCF.sub.3        1-5                                                                              Methylcellosolve                                                                       20 H(CF.sub.2).sub.6 CF═CF.sub.2 5.0                                                    Benzoyl                                                                            0.3                                                                             -- *.sup.3 100 .sup.                                                                  6  HOCHCH.sub.2 OCH.sub.3,                                     peroxide            CF.sub.2 CHF(CF.sub.2).sub.6                                                 H                                                                            HOCH.sub.2 CHOCH.sub.3                                                           CF.sub.2 CHF(CF.sub.2).sub.                                                6 H                                                                           HOCH.sub.2 CH.sub.2 OCH.sub.2                                                 CF.sub.2 CHF(CF.sub.2).sub.6      __________________________________________________________________________                                                H                                  *.sup.3 normal pressure                                                  

                Boiling                                                           Exam-                                                                             Yield   point   Elemental Analysis                                        ple (yield %)*.sup.1                                                                      °C./mm Hg                                                                      C (%) H (%) F (%)                                                                       GC-MS analysis                                                                         IR                                     __________________________________________________________________________    1-2 18.5 g (61.7%)                                                                        110--110/1                                                                            (Calculated                                                                             FI method                                                                              νOH3330 cm.sup.-1 S,                                                       ν-CH.sub.2 2900 cm.sup.-1                               36.00,.sup.  4.67,  37.97)                                                              Molecular                                                           Found     ion mass                                                                            301                                                                              νCF1200 cm.sup.-1, νC--O--C                                             1100 cm.sup.-1                                             36.4, .sup.  4.4,   38.2                                  1-3 15.2 g (72.0%)                                                                          43-69/26-10                                                                         (Calculated                                                                             FI method                                                                              νOH3400 cm.sup.-1 S,                                                       ν-CH.sub.2 2920 cm.sup.-1,                                                 νCH.sub.3                                               31.84,.sup.  3.54,  50.4)                                                               Molecular                                                           Found     ion mass                                                                            227                                                                              2880 cm.sup.-1, νCF1200                                                    cm.sup.-1, νC--O--C 1100                                                   cm.sup.-1                                                  30.6, .sup.  3.3,   51.2                                  1-4 21.3 g (67.8%)                                                                          89-98/1                                                                             (Calculated                                                                             FI method                                                                              νOH3370 cm.sup.-1 S,                                                       ν-CH.sub.2 2920 cm.sup.-1,                                                 νCH.sub.3                                               38.19,.sup.   5.09,  36.28)                                                             Molecular                                                           Found     ion mass                                                                            315                                                                              2880 cm.sup.-1, νCF1200                                                    cm.sup.-1, νC--O--C 1100                                                   cm.sup.-1                                                  37.3, .sup.  4.8,   38.1                                  1-5  5.6 g (93.4%)                                                                           --   (Calculated                                                                             FI method                                                                              νOH3380 cm.sup.-1 S,                                                       ν-CH.sub.2 2920 cm.sup.-1,                                                 νCH.sub.3                                               28.81,.sup.  1.96,  62.21)                                                              Molecular                                                           Found     ion mass                                                                            459                                                                              2890 cm.sup.-1, νCF 1200                                                   cm.sup.-1, νC--O--C 1130                                                   cm.sup.-1                                                  29.8, .sup.  1.9,   61.0                                  __________________________________________________________________________     *.sup.1 based on fluoroolefin mol %                                      

    Example                             .sup.1 H NMR (solvent for measurement                                         CDCl.sub.3)                               __________________________________________________________________________                                   1-2  δ = 3.68-4.50                                                           (Triethyleneglycol portion C .sub.--                                          H.sub.2 C .sub.-- H)                                                          δ = 5.20 Doublet multiplet                                                 (--CF .sub.-- H.sup.2 J.sub.HF =                                           42 Hz, .sup.3 J.sub.HF =  7 Hz)                                          1-3  δ = 3.38-3.40 (OC .sub.--                                               H.sub.3)                                                                      δ = 5.0 Doublet multiplet                                                  (--CF .sub.-- H.sup.2 J.sub.HF =                                           42 Hz, .sup.3 J.sub.HF = 7 Hz)                                                δ = 3.40-4.50  .sub.-- HOC                                              .sub.-- H.sub.2 C .sub.-- H.sub.2 OC                                          .sub.-- H.sub.2 -Rf*.sup.4                                                            .sub.-- HOC .sub.-- HC                                                .sub.-- H.sub.2 OC .sub.-- H.sub.3                                                   Rf*.sup.4                                                                      .sub.-- HOC .sub.-- H.sub.2 C                                         .sub.-- HOC .sub.-- H.sub.3                                                          Rf*.sup.4                                                         1-4  δ = 3.21 (OC .sub.-- H.sub. 3)                                          δ = 3.3-4.5 (Triethyleneglycolmo                                        nomethylether portion                                                               C .sub.-- H.sub.2, C .sub.-- H,                                         O .sub.-- H)                                                                  δ = 5.10 Doublet multiplet                                                 (--C .sub.-- HF.sup.2 J.sub.HF =                                           42 Hz, .sup.3 J.sub.HF = 7 Hz)                                           1-5  δ = 3.40 (OC .sub.-- H.sub.3)                                           δ = 3.4-5.9 (Methylcellosolve                                           portion C .sub.-- H.sub.2, C .sub.--                                          H, O .sub.-- H)                                                               δ = 6.0 triplet-triplet                                                    (.sup.2 J.sub.HF ≈ 68 Hz,                                          .sup.3 J.sub.HF ≈ 5 Hz                                                CF.sub.2  .sub.-- H)                                                          δ = 7.7 doublet multiplet                                                  (.sup.2 J.sub.HF ≈ 50 Hz,                                          .sup.3 J.sub.HF ≈ 7 Hz                                                CF.sub.2  .sub.-- H                       __________________________________________________________________________     *.sup.4 --CF.sub.2 CHFCF.sub.3                                           

Example 1-6

A 300 ml eggplant type flask was charged with 40 g of polyethyleneglycol (average molecular weight: 3,000), 7 ml (31.1 mol) of 8-Hperfluorooctene-1, 1.0 g (4.1 mmol) of benzoyl peroxide, and 40 ml ofchlorobenzene as a solvent, and the mixture was stirred at 100° C. for 5hours under a nitrogen atmosphere. The solvent was removed from thereaction product by a rotary evaporator, the remaining product was driedat 100° C. with a vacuum pump, 300 ml of tetrahydrofuran was addedthereto, and reprecipitation was effected with 3 liters of hexane withice cooling under a nitrogen atmosphere. The precipitates obtained werefiltered under a nitrogen atmosphere, followed by drying for severalhours with a vacuum pump, to obtain 51.62 g of the desired polyethyleneglycol derivative having fluoroalkyl group (yield: 98.5%).

IR 3425 cm⁻¹ νOH, 2900 cm⁻¹ ν--CH₂, 1470 cm⁻¹ νCH₂, 1210 cm⁻¹ νCF, 1120cm⁻¹ νC--O--C

¹ H-NMR (solvent for measurement: CDCl₃)

δ=3.68 (ethylene glycol portion CH₂)

δ=5.32 (--CFH--)

δ=6.05 Triplet

(CF₂ H--² J=50 Hz)

¹³ C-NMR (solvent for measurement: CDCl₃)

δ=61.4 (HOCH₂ CH₂ O--)

δ=70.4 (--OCH₂ CH₂ O--)

δ=72.3 (HOCH₂ CH₂ O--)

δ=100-125 (--CF_(n) --)_(n) =1 or 2

¹⁹ F-NMR (solvent for measurement)

δ=-210--213 (CF₂ H)

δ=-136 (doublet)

J_(FH) =50 Hz (--CFH--)

δ=-128 (CF₂ H CF₂ --)

δ=-114--122 (--CF₂ CFH(CF₂)₄ CF₂ CF₂ H)

GPC peak:

6.32×10³

272×10⁴

Mw/Mn=2.25

Ion chromatography

F content: 15.4% by weight

Glass transition temperature

Tm (°C.): 48.1

Crystallinity (%): 53.3

From the IR and NMR analytical results, it was determined that thestructure is represented by the formula: ##STR21## and from the averagemolecular weight and the F content, it was determined that the number ofgrafted fluoroalkyl groups is 1.6 and (CH₂ CH₂ O)_(m) and ##STR22## arearranged at random.

Since the values of Tm and crystallinity are lower than those ofComparative Example 1-1, it is understood that the obtained derivativeis grafted.

Example 1-7

The same procedures as in Example 6 were conducted, except that 20 ml(88.9 mmol) of 8-H perfluorooctene-1 was used in Example 6 to obtain69.3 g of a polyethylene glycol derivative having a fluoroalkyl group.The results are shown in Table 1-2.

Comparative Example 1-1

The same procedures as in Example 1-6 were conducted except that the 8-Hperfluorooctene-1 used in Example 1-6 was omitted.

The results are shown in Table 1-2.

                  TABLE 1-2                                                       ______________________________________                                                                 Comparative                                                       Example 1-7 Example 1-1                                          ______________________________________                                        Average molecular weight                                                                     5900          5700                                             (GPC, in terms of                                                                            --CF.sub.2 CHF(CF.sub.2).sub.6 H                                                            --                                               polystyrene)                                                                  F content (% by weight)                                                                      30.9          0                                                (ion chromatographic                                                          analysis)                                                                     Number of grafted groups                                                                     3.3           0                                                Tm °C.  42.7          53.1                                             Crystallinity  32.5          73.5                                             ______________________________________                                    

Example 1-8

Into a 200 ml stainless steel autoclave 48 g of n-octane diol, 5.0 g ofdi-tert. butyl peroxide, and 70 ml of benzotrifluoride as a solvent werecharged and, after sealing, 122 g hexafluoropropylene was charged underpressure, followed by allowing to react the mixture, while stirring, at130° C. for 7 hours.

After completing the reaction, the reaction mixture was cooled and thenthe gas in the autoclave was purged, followed by withdrawing thereaction mixture therefrom. The reaction mixture was concentrated undera reduced pressure and the solvent was distilled off. The residue wasextracted with diethyl ether, followed by repeatedly washing with water.The ether layer was separated. Thereafter, the residue was concentratedto isolate 48 g of the crude product. The crude product was furtherdistilled under a reduced pressure to obtain 38 g of 1 or 2 or 3 or4-hexafluoropropyl-1,8 octane diol isomers.

The physical properties and analytical data of the product are shown inTable 1-3.

Example 1-9

The same procedures as in Example 1-8 were conducted except that 150 gof n-pentane diol, 16 g of di-tert. butyl peroxide, 110 ml of abenzotrifluoride solvent, and 120 g of hexafluoropropylene were used.Thus, 152 g of 1 or 2 or 3-hexafluoro-1,5-pentanediol isomers wereobtained.

The results are shown in Table 1-3.

Example 1-10

The same procedures as in Example 1-8 were conducted except that 14 g ofn-butane diol, 0.8 g of di-tert. butyl peroxide, 10 ml of abenzotrifluoride solvent, and 16 g of hexafluoropropylene were used.Thus, 9.0 g of 1 or 2-hexafluoropropyl-1,4-butane diol was obtained.

The physical properties and analytical data of the product are shown inTable 1-3.

                                      TABLE 1-3                                   __________________________________________________________________________                                                      Elemental                                                                     analysis (%)                     Field *1                                                                           Boiling point                  I.R.     Found                       Example                                                                            (%)  (°C./mmHg)                                                                     Product                (neat. cm.sup.-1)                                                                      (calculated)                                                                         .sup.13              __________________________________________________________________________                                                             C-NMR                1-8  39.2 142-158/5                                                                              ##STR23##             νOH 3300-3400 νCF                                                                C 45.2 (44.6) H  5.6                                                          (6.1) F 39.2                                                                         *28.5)               1-9  41.3 122-139/3                                                                              ##STR24##             νOH 3300-3400 νCF                                                                C 36.2 (37.8) H  4.3                                                          (4.7) F 46.1                                                                         *34.9)                1-10                                                                              34.0 80-92/3                                                                                ##STR25##             νOH 3300-3400 νCF                                                                C 34.6 (35.0) H  4.1                                                          (4.2) F 49.0                                                                         --7.5)               __________________________________________________________________________    *1 based on the diol                                                          *2 .sup.13 C NMR (Example 1-8)                                                δ (ppm)                                                                         Moiety                                                                18-20   HOCC .sub.--CH.sub.2                                                  30.5, 31.3                                                                             ##STR26##                                                            31.9, 32.1                                                                             ##STR27##                                                            33-36                                                                                  ##STR28##                                                            32.5, 33.8                                                                             ##STR29##                                                            45.8, 46.4                                                                             ##STR30##                                                            57.5-59.1                                                                              ##STR31##                                                            61.8, 64.3, 64.5                                                                       ##STR32##                                                            66.3, 68.5                                                                             ##STR33##                                                            82.3-86.2                                                                              ##STR34##                                                            116.3, 116.9                                                                           ##STR35##                                                            120.0                                                                                  ##STR36##                                                                     ##STR37##                                                            *3 .sup.13 C NMR (Example 1-9)                                                δ (ppm)                                                                         Moiety                                                                23.6    HOCH.sub.2 CH.sub.2  .sub.--CH.sub.2                                  28.3    HOCH.sub.2 CH.sub.2 CH.sub.2  .sub.--CH.sub.2                         32.8    HOCH.sub.2  .sub.--CH.sub.2 CH.sub.2                                  44-45                                                                                  ##STR38##                                                            61.8    HO .sub.--CH.sub.2 CH.sub.2                                           67.3-68.7                                                                              ##STR39##                                                            83.0-86.0                                                                              ##STR40##                                                            113-118                                                                                ##STR41##                                                            118-125                                                                                ##STR42##                                                            __________________________________________________________________________

Example 2-1

In a 100 ml flask were mixed, while stirring 6.0 g of1,2-dihydroxy-3,3,4,5,5,5-hexafluoropentane, 10.3 g of methacrylic acidchloride, and 60 ml of tetrahydrofuran as a solvent, and 11.5 g oftriethylamine was slowly added to the mixture dropwise under ice coolingover 1 hour. Subsequently, the mixture was allowed to react at 50° C.for 2 hours while stirring, methanol was added dropwise to the reactionmixture to decompose excessive methacrylic acid chloride, the reactionmixture was then filtered, and the filtrate was concentrated under areduced pressure to obtain a crude product. Ethyl ether was added to theproduct obtained and the mixture was again filtered, and ether wasevaporated from the filtrate under a reduced pressure, to obtain 9.3 gof the desired ethylene glycol dimethacrylate having fluoroalkyl group:##STR43## (GC purity: 98%).

    ______________________________________                                        Elemental analytical values                                                            C (%)      H (%)   F (%)                                             ______________________________________                                        Calculated 44.83        4.02    32.76                                         Found      45.1         4.3     31.9                                          ______________________________________                                    

Gas chromatographic analysis

According to the FI method the molecular ion peak+1 mass was 349.

IR analysis chart is shown in FIG. 1.

νCO₂ 1720 cm⁻¹, νCH₂ =C- 1630 cm⁻¹, νC-F 1200 cm⁻¹

¹ H-NMR analytical value (solvent for measurement: CDCl₃) ##STR44##

Example 2-2

The same procedures as in Example 2-1 were conducted except that analkylene glycol grafted with fluoroalkyl group 7.1 g having a mixture ofisomers of triethylene glycol in which one --CH₂ CFHCF₃ group isgrafted, ##STR45## 6.6 g of methacrylic acid chloride and 7.4 g oftriethylamine were used, to obtain 7.3 g of the desired triethyleneglycol dimethacrylate having a fluoroalkyl group:

    ______________________________________                                        Elemental analytical value                                                             C (%)      H (%)   F (%)                                             ______________________________________                                        Calculated 46.79        5.05    26.15                                         Found      45.3         4.8     27.5                                          ______________________________________                                         Gas chromatographic analysis

According to the FI method the molecular ion peak+1 mass was 437.

IR analytical value

νCO₂ 2950 cm ⁻¹, νCO₂ 1720 cm⁻¹, νC═C 1640 cm ⁻¹, νCF 1160-1220 cm ⁻¹,νC--O--C 1100 cm ⁻¹

¹ H-NMR analytical value (solvent for measurement: CDCl₃) ##STR46##

Example 2-3

The same procedures as in Example 2-1 were conducted except that analkylene glycol containing fluoroalkyl group 9.7 g of mixture of methylcellosolve having a ##STR47## 6.0 g of methacrylic acid chloride, and6.4 g of triethylamine were used, to obtain 9.5 g of the desiredmonomethacrylate having fluoroalkyl group: ##STR48##

    ______________________________________                                        Elemental analytical values                                                            C (%)      H (%)   F (%)                                             ______________________________________                                        Calculated 40.82        4.08    38.78                                         Found      39.6         3.9     37.9                                          ______________________________________                                         Gas chromatographic analysis

According to the FI method the molecular ion peak+1 mass was 295.

IR analytical value

νCH₂ 2920 cm ⁻¹, νCH₃ 2880 cm⁻¹, νCO₂ 1720 cm⁻¹, νC═C' 1635 cm⁻¹, νCF1160-1220 cm⁻¹, νC--O--C 1100 cm⁻¹

¹ H-NMR analytical value (solvent for measurement: CDCL₃) ##STR49##

Example 2-4

A 1 liter four-necked flask was charged with 40 g of fluoroalkylatedpolyethylene glycol having --CF₂ CHF(CF₂)₆ H group (Mn: 6.2×10³, Fcontent: 15.4% by weight), 200 ml of trimethylamine, 200 ml of pyridine,and 200 ml of chloroform as a solvent, and 10 ml of methacrylic acidchloride was slowly added dropwise to the mixture under a nitrogenatmosphere. After completion of the dropwise addition, the temperaturewas elevated to 70° C. and the reaction was carried out for 1 hour. Tothe ice-cooled reaction mixture was added 100 ml of methanol, themixture obtained was stirred at 40° C. for 1 hour to effectmethylesterification of excessive methacrylic acid chloride, andthereafter, reprecipitation was carried out with 5 liters of ice-cooledhexane under a nitrogen atmosphere and the precipitates were filtered ata low temperature, 300 liters of THF were added thereto, and the mixturewas filtered to remove insolubles. To the filtrate was added 1 g ofp-methoxyphenol as a polymerization inhibitor, and the mixture wasreprecipitated with 5 liters of hexane under ice cooling. Theprecipitates were filtered at a low temperature and then washedthoroughly with hexane, followed by drying for 3 hours with a vacuumpump, to obtain 32 g of the desired dimethacrylate derivative.

Ion chromatographic analysis:

F content: 12.8% by weight

G.P.C. analysis:

Mn=7.8×10³

Tm (°C.): 50 (DSC analysis)

IR analytical values: ν--CH₂ 2900 cm⁻¹, νC═C 1735 cm⁻¹, νC═C 1640 cm⁻¹,νC--F 1210 cm⁻¹, νC--O--C 1120 cm⁻¹

¹ H-NMR analytical values (solvent for measurement: CDCl₃) ##STR50##

(¹³ C-NMR analytical values (solvent for measurement CDCL₃) ##STR51##

¹⁹ F-NMR analytical values (solvent for measurement: CDCL₃)

δ≅-210--213 (CF₂ H)

δ≅-136 (--CFH--JFH≅50 Hz)

δ≅-128 CF₂ HCF₂ --)

δ≅-144--122 (--CF₂ CHF(CF₂)₄ CF₂ CF₂ H)

From the IR and NMR analytical results, it was determined that thestructure is represented by the formula: ##STR52## and based on thecalculation of the average molecular weight and the F content, it wasdetermined that the number of grafted fluoroalkyl groups is 2.0 and##STR53## are arranged at random.

Since the Tm value is lower than that of Comparative Example 2-1, it isunderstood that the obtained derivative is grafted.

Example 2-5

The same procedures as in Example 4 were conducted except thatfluoroalkylated polyethylene glycol having a --CF₂ CHF(CF₂)₆ H group(Mn: 5.9×10³, F content: 30.9% by weight) was used to obtain 34 g of thedesired dimethacrylate derivative.

According to the IR and NMR analytical results, the same absorptionproperty as that of Example 2-4 was observed. The other results areshown in Table 2-1.

Example 2-6

A 1 liter four-necked flask was charged with 110 g of fluoroalkylatedpolyethylene glycol having --CF₂ CHFCF₃ group (Mn: 7.7×10³, F content:9.2% by weight), 30 g of methacrylic acid chloride, and 500 ml oftetrahydrofuran as a solvent, and 60 of triethylamine was slowly addeddropwise to the mixture under a nitrogen atmosphere. The same proceduresas in Example 2-4 were conducted thereafter to obtain 83 g of thedesired dimethacrylate derivative.

The analytical values are shown in Table 2-1.

Example 2-7

The same procedures as in Example 2-4 were conducted except that afluoroalkylated polyethylene glycol having a --CF₂ CHFCF₃ group (Mn:18.0×10³, F content: 18.8% by weight) was used to obtain 36 g of thedesired dimethacrylate derivative.

The analytical values are shown in Table 2-1.

Comparative Example 2-1

The same procedures as in Example 2-4 were conducted except thatpolyethylene glycol (Mn: 6.5×10³) was used to obtain 34 g of the desireddimethacrylate derivative.

The analytical values are shown in Table 2-1.

                                      TABLE 2-1                                   __________________________________________________________________________                                              Comparative                                         Example 2-5                                                                             Example 2-6                                                                           Example 2-7                                                                           Example 2-1                         __________________________________________________________________________    Average molecular weight                                                                      7076      7910    18700   6000                                (GPC calculated on polystyrene)                                               Kind of grafted functionality                                                                 --CF.sub.2 CHF(CF.sub.2).sub.6 H                                                        --CF.sub.2 CHFCF.sub.3                                                                --CF.sub.2 CHFCF.sub.3                                                                --                                  F content (wt. %)                                                                             27.7      7.9     18.5    0                                   (Ion chromatographic analysis)                                                Tm °C.   44.6      42.0    39.0    53.1                                __________________________________________________________________________

Example 2-8

A 100 ml four-necked flask was charged with 20.3 g of polypropyleneglycol grafted with --CF₂ CHFCF₃ group (Mn: 4.5×10³, F content: 8.5% byweight), 7.0 g of methacrylic acid chloride, and 50 ml oftetrahydrofuran as a solvent, followed by stirring under ice cooling,and 14 g of triethylamine was slowly added dropwise to the mixture. Thetemperature was then elevated to 60° C., and the reaction was carriedout for 1 hour. To the reaction mixture, which had been again icecooled, 7.0 ml of methanol was slowly added dropwise, and the mixturewas allowed to react at 40° C. for 1 hour. The reaction mixture wasfiltered and the filtrate was concentrated, followed by vacuum drying,to obtain 18.3 g of the desired liquid dimethacrylate derivative.

The average molecular weight calculated on polystyrene according to GPCanalysis was Mn: 4.4×10³, and the F content according to ionchromatographic analysis was 7.9% by weight. The IR analysis showed thatthe derivative had the absorption properties of νCH₂ 2900 cm⁻¹, νCH ₃2850 cm⁻¹, νC═O 1720 cm⁻¹, νC═C 1640 cm⁻¹, νC--F 1180-1210 cm⁻¹,νC--O--C 1100 cm⁻¹.

According to ¹ H NMR analysis (solvent for measurement: CDCl₃), thefollowing signals were observed. ##STR54##

From these results, it was formed that the product has the structurerepresented by: ##STR55## in which the l, m, n, o and p groups arearranged at random.

Example 2-9

In a 500 ml flask were mixed, while stirring, 34 g of an isomer mixtureof 1 or 2 or 3 or 4-hexafluoropropyl-1,8-octane diol, 36 g ofmethacrylic acid chloride, and 200 ml of a tetrahydrofuran solvent, and55 g of htriethylamine was slowly added to the mixture dropwise underice cooling over 2 hours. Subsequently, the mixture was allowed to reactat room temperature for 2 hours while stirring. The methanol was addeddropwise to the reaction mixture to decompose excessive methacrylic acidchloride, the reaction mixture was then filtered, and the filtrate wasconcentrated under a reduced pressure to obtain a curde product. Ethylether was added to the crude product obtained and the mixture was againfiltered, and ether was distilled off from the filtrate under a reducedpressure, to obtain 37 g of the desired octane dimethacrylate having ahexafluoropropyl group.

The analytical results are shown in Table 2-2.

Example 2-10

The same procedures as in Example 2-9 were conducted except that 28.6 gof an isomer mixture of 1 or 2 or 3-hexafluoropropyl-1,5-pentane diol,37.5 g of methacrylic acid chloride, 200 ml of tetrahydrofuran as asolvent, and 57.7 g of triethylamine were used. Thus, 27.6 g of thedesired pentane dimethacrylate having a hexafluoropropyl group wasobtained.

The results are shown in Table 2-2.

Example 2-11

The same procedures as in Example 2-9 were conducted except that 7.0 gof an isomer mixture of 1 or 2-hexafluoropropyl-1,4-butane diol, 6.5 gof methacrylic acid chloride, 100 ml of tetrahydrofuran as a solvent,and 9.7 g of triethylamine were used. Thus, 8.6 g of the desired butanedimethacrylate having a hexafluoropropyl group was obtained.

The results are shown in Table 2-2.

                                      TABLE 2-2                                   __________________________________________________________________________                                                      Elemental                                                                     analysis (%)                                                   G.C.  I.R.     Found                       Example                                                                            Field (%)                                                                           Product                 purity (%)                                                                          (neat. cm.sup.-1)                                                                      (calculated)                                                                         .sup.13 C            __________________________________________________________________________                                                             NMR                  2-9  74.6                                                                                 ##STR56##              98.6  νCO.sub.2 νCH.sub.2C                                                    νCF                                                                              1720 1630 1200                                                                   C 52.3 (52.8) H  6.1                                                          (6.0) F 25.0                                                                         *16.4)                           ##STR57##                                                         2-10 62.9                                                                                 ##STR58##              96.9  νCO.sub.2 νCH.sub.2C                                                    νCF                                                                              1720 1638 1200                                                                   C 49.0 (49.2) H  5.3                                                          (5.1) F 29.6                                                                         *29.2)               2-11 84.0                                                                                 ##STR59##              92.6  νCO.sub.2 νCH.sub.2C                                                    νCF                                                                              1720 1640 1200                                                                   C 47.7 (47.9) H  4.9                                                          (4.8) F 30.7                                                                         --0.3)               __________________________________________________________________________    *1 .sup.13 C NMR (Solvent: CDCl.sub.3, Standard: 77.0 (CDCl.sub.3))                      ##STR60##                                                          δ (ppm)                                                                           Moiety                                                              17.7                                                                                     ##STR61##                                                          25.6                                                                                     ##STR62##                                                          28.3                                                                                     ##STR63##                                                          28.8                                                                                     ##STR64##                                                          40-41.                                                                                   ##STR65##                                                          64.3                                                                                     ##STR66##                                                          69.8-71.2                                                                                ##STR67##                                                          83-85.8                                                                                  ##STR68##                                                          113-118                                                                                  ##STR69##                                                          118-125                                                                                  ##STR70##                                                          124.5, 126.8, 129.9.                                                                     ##STR71##                                                          134.0, 135.0, 136.2.                                                                     ##STR72##                                                          163.5, 163.6, 165.2, 165.4, 167.0.                                                       ##STR73##                                                          *2 .sup.13 C NMR (Solvent: CDCl.sub.3, Standard: 77.0 (CDCl.sub.3))                      ##STR74##                                                          δ (ppm)                                                                           Moiety                                                              17.4-17.8                                                                                ##STR75##                                                          20, 21.2, 21.3, 22                                                                       ##STR76##                                                          26.5, 27.3                                                                               ##STR77##                                                          27.9, 28.1                                                                               ##STR78##                                                          29.0-32                                                                                  ##STR79##                                                          34.5, 35.8                                                                               ##STR80##                                                          41.8, 42.4                                                                               ##STR81##                                                          60-61.6                                                                                  ##STR82##                                                          63.8-64.4                                                                                ##STR83##                                                          66.8, 67.0                                                                               ##STR84##                                                          68.8, 71.0                                                                               ##STR85##                                                          82.3-86.2                                                                                ##STR86##                                                          116.2, 116.8                                                                             ##STR87##                                                          120.5                                                                                    ##STR88##                                                          124.7, 126.8, 128.3                                                                      ##STR89##                                                          135.3, 135.7, 136.4                                                                      ##STR90##                                                          165.3, 165.6, 167.2                                                                      ##STR91##                                                      

We claim:
 1. A mono- or poly-oxyalkylene glycol acrylate of the formula(V) ##STR92## wherein R⁴ represents hydrogen or methyl;R¹, R² and R³independently represent hydrogen or an alkyl group having 1 to 30 carbonatoms; x represents an integer of 0 to 100; and n represents an integerof 1 to 1000; the mono- or poly-oxyalkylene group in the main chain ofsaid mono- or poly-alkylene glycol having at least onefluorine-substituted hydrocarbon group with 2 to 30 carbon atoms havingat least 3 fluorine atoms bonded thereto graft-bonded onto the mono- orpoly-oxyalkylene group in the main chain of the mono- orpoly-oxyalkylene group in the main chain of the mono- or poly-alkyleneglycol per one molecule of the mono- or poly-alkylene glycol.